CN1100612C - Fluidized bed catalyst for oxidation of propene ammonia - Google Patents
Fluidized bed catalyst for oxidation of propene ammonia Download PDFInfo
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- CN1100612C CN1100612C CN99113987A CN99113987A CN1100612C CN 1100612 C CN1100612 C CN 1100612C CN 99113987 A CN99113987 A CN 99113987A CN 99113987 A CN99113987 A CN 99113987A CN 1100612 C CN1100612 C CN 1100612C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a fluid bed catalyst for preparing acrylonitrile by propylene ammoxidation. The present invention contains silicon dioxide carriers and a composition with the following chemical formula by atomic ratio: Mo12BiaFebSbcSrdXeYfZgOh, X is at least one of Co, Ni, Mn, Mg, Ca, Zn and Cd, Y is at least one of P, W, Ge, V, Cr, Ce, Pr, Nb and Tb, and Z is at least two of alkali metals, In, Tl, Sm and Te. The present invention is particularly suitable for being used under the conditions of a high reaction pressure and a high propene load; high single-pass yield of acrylonitrile can be kept, and the present invention can be used for industrial production.
Description
The present invention relates to a kind of fluid catalyst of ammoxidating propylene to produce acrylonitrile.
Acrylonitrile is important Organic Chemicals, and it is produced by the ammoxidation of propylene reaction.For obtaining the fluid catalyst of high activity, high selectivity, people have carried out a series of improvement through constantly exploring.These improve and mostly relate to catalyst activity partly, pay attention to the collocation between the catalyst activity component, and improve activity of such catalysts and selectivity, thereby reach the raising of acrylonitrile once through yield, and the raising of producing load.
Ammonia oxidation is produced acrylonitrile through 30 years of development, and the production capacity of factory and the market demand are near balance.The main development tendency of acrylonitrile process has been turned to the transformation of original factory, further to cut down the consumption of raw materials and to increase production capacity by the construction new equipment at present.By transformation to original factory, change the bottleneck in effective catalyst and the elimination production technology, the production capacity of acrylonitrile might improve 50～80%, and required investment only is 20～30% of a new device, economic benefit is very huge.
Can produce two problems during factory transforms: 1. the reaction pressure of fluidized-bed reactor will rise; 2. the useful load of catalyst can not be too many.The catalyst that for this reason requires to use instead should have higher propylene load and can bear higher reaction pressure.
The reaction pressure of fluidized-bed reactor is to be determined to the resistance drop that absorbs a series of heat exchangers, tower and pipe arrangement the cat head by reactor outlet.Because the increase of production capacity obviously increases the inventory of reactor outlet, above-mentioned resistance drop is increased.In addition, each heat exchanger heat transfer area also need increase heat transmission equipment inadequately, and resistance drop is further increased.Because environmental requirement, the reactor off-gas that absorbs cat head is forbidden directly to be discharged in the atmosphere, deliver to stove and burn.If like this without air-introduced machine, then must improve the absorption tower top pressure.For all the foregoing reasons, the operating pressure of reactor will increase by 0.5～1.0 times than design load at present, promptly reaches more than the 0.08MPa.
Above-mentioned second load that problem is a catalyst, i.e. WWH.Its definition is a catalyst per ton, per hour can handle what ton propylene.Because the increase of reactor feed amount, if the load of catalyst is constant, then the catalyst useful load is also wanted corresponding increase.But cooling water pipe insufficient height in the intrinsic fluidized-bed reactor, so the fluid height of catalyst reactor might surpass the height of cooling water pipe.In addition, because the increase of reactor feed amount, so operating linear velocity also significantly improves.The combined influence of these two variations might make reactor dilute phase temperature rise, and causes carbon dioxide production to increase, and the acrylonitrile selectivity descends.Therefore the WWH of catalyst is higher can prevent the problems referred to above.
The WWH that improves catalyst in theory should increase the adsorption capacity of catalyst to propylene, but at present still in the catalyst-free certain element can improve theory to the propylene adsorption capacity.The catalyst of following composition has been proposed in document CN1021638C:
A
aB
bC
cNi
dCo
eNa
fFe
gBi
hM
iMo
jO
x
Wherein A is potassium, rubidium, caesium, samarium, thallium; B is manganese, magnesium, strontium, calcium, barium, lanthanum, rare earth element; C is phosphorus, arsenic, boron, antimony, chromium; M is tungsten, vanadium.
Above-mentioned catalyst can obtain higher single-pass yield of acrylonitrile, but the propylene of catalyst load is lower, and single-pass yield of acrylonitrile descends bigger under higher reaction pressure.Studies show that further the B component in the above-mentioned catalyst is relevant with performance under high pressure to the load of catalyst with M.Though some element in the B component has effect to improving single-pass yield of acrylonitrile, and the raising of catalyst loading and the performance of high-response pressure are had negative effect, be unfavorable for that catalyst adapts to elevated pressures, operates under the higher load condition.Once in stipulating in CN1021638C in addition that above-mentioned catalyst was formed, the summation of i and j is 12, promptly is a constant.Cancel this regulation in the present invention,, will influence single-pass yield of acrylonitrile because molybdenum component will reduce when increasing by this regulation M component.
The objective of the invention is to overcome the catalyst that exists in the above-mentioned document and can not adapt to problem, a kind of new fluidized bed catalyst for ammoxidation of propylene is provided than high-response pressure and operational load.This catalyst can adapt under higher reaction pressure and higher loading condiction to be operated, and keeps high acrylonitrile once through yield.
The objective of the invention is to realize by following technical scheme: a kind of fluidized bed catalyst for ammoxidation of propylene, form by silica supports with the following composition of atomic ratio measuring chemical formula:
Mo
12Bi
aFe
bSb
cSr
dX
eY
fZ
gO
h
X is selected among Co, Ni, Mn, Mg, Ca, Zn or the Cd at least a in the formula;
Y is selected among P, W, Ge, V, Cr, Ce, Pr, Nb or the Tb at least a;
Z is selected among alkali metal, In, Tl, Sm or the Te at least a;
The span of a is 0.01～3.0;
The span of b is 0.1～5.0;
The span of c is 0.01～2.0;
The span of d is 0.01～2.0;
The span of e is 0.1～12;
The span of f is 0.01～3.0;
The span of g is 0.01～1.5;
H satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein the amount of carrier silica is 30～70% by weight percentage in the catalyst.
The value preferable range of c is 0.05～1.0 in the technique scheme, and the value preferable range of d is 0.05～0.1, and the value preferable range of e is 0.1～10.0, and the value preferable range of f is 0.1～2.0, and the value preferable range of g is 0.05～1.0.In the carrier amount of silica by weight percentage preferable range be 40～60%.
The manufacture method of catalyst of the present invention there is no specific (special) requirements, can be undertaken by well-established law.At first the catalyst each component is made solution, be mixed and made into slurry with carrier again, the spray-dried microspheroidal that is shaped to, catalyst is made in last roasting.The preparation of slurry is preferably undertaken by the CN1005248C method.
The raw material of making catalyst of the present invention is:
Molybdenum component in the catalyst is with molybdenum oxide or ammonium molybdate.
Bismuth in the catalyst, iron, strontium can maybe can be decomposed into the salt of oxide with nitrate, oxide, but preferably use water miscible nitrate.
The antimony component can be used antimony oxide in the catalyst, and antimony pentaoxide, hydrolysis can generate the antimony halides or the antimony colloidal sol of antimony oxide.
The most handy nitrate of component X, hydroxide maybe can be decomposed into the salt of oxide.
The most handy corresponding acids of phosphorus among the component Y or its ammonium salt, tungsten can be with ammonium tungstate or tungsten oxide, and vanadium can be used ammonium metavanadate; Its oxide of germanium; The most handy chromium trioxide of chromium, chromic nitrate or the mixture of the two; Cerium, praseodymium, rubidium and terbium can maybe can be decomposed into the salt of oxide with its nitrate.
Raw material available silicon colloidal sol, silicon gel or both mixtures as the silica of carrier.If use Ludox, its quality will meet the requirement of CN1005248C.
It is 47～55% back spray-dryings that the prepared slurry heating is concentrated to solid content.Spray dryer available pressure formula, two streamings or centrifugal turntable formula, but, can guarantee that the catalyst of making has good size distribution with centrifugal better.
The roasting of catalyst can be divided into two stages and carry out: each element decomposition of salts and high-temperature roasting in the catalyst.The catabolic phase temperature is preferably 200～300 ℃, and the time is 0.5～2 hour.Sintering temperature is 500～800 ℃, is preferably 550～700 ℃; Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out respectively in two roasters, also can be divided into two zones in a stove, also can finish simultaneously in the continous way rotary roasting furnace and decompose and roasting.In catalyst decomposes and roasting process, to feed an amount of air, prevent that catalyst is by over reduction.
Adopt the specification of catalyst manufacturing acrylonitrile of the present invention required propylene, ammonia and molecular oxygen identical with other ammoxidation catalyst of use.Though the low molecule saturated hydrocarbon content in the raw material propylene to the reaction did not influence, considers that from economic point of view density of propylene is more preferably greater than 85% (mole).Ammonia can be used fertilizer grade liquefied ammonia.Reaction desired molecule oxygen can be used pure oxygen from technical standpoint, oxygen enrichment and air, but from economy and the most handy air of security consideration.
Entering the ammonia of fluidized-bed reactor and the mol ratio of propylene is between 0.8～1.5, is preferably 1.0～1.3.The mol ratio of air and propylene is 8～10.5, is preferably 9.0～9.8.If owing to some operational reason must with higher air than the time, can increase to 11, reaction is not had significant impact.But from security consideration, the excess of oxygen in the reacting gas can not preferably be not more than 4% greater than 7% (volume).
When catalyst of the present invention was used for fluidized-bed reactor, reaction temperature was 420～470 ℃, was preferably 430～450 ℃.Therefore catalyst of the present invention is a kind of high pressure, high load capacity catalyst of being applicable to, reaction pressure can be more than 0.08MPa in process units, for example, and 0.08～0.15MPa.Also do not have any adverse effect if reaction pressure is lower than 0.08MPa, single-pass yield of acrylonitrile can further improve.
The propylene load (WWH) of catalyst of the present invention is 0.06～0.15 hour
-1, be preferably 0.07～0.10 hour
-1Loading to hang down not only wastes catalyst, and carbon dioxide production is increased, and selectivity descends, and is disadvantageous.Loading does not too highly have practical significance, because the catalyst addition is very few, the heat transfer area that can make cooling water pipe in the catalyst layer causes reaction temperature uncontrollable less than removing the required area of reaction heat.
The product of making acrylonitrile with catalyst of the present invention reclaims process for refining, and available existing production technology need not done any transformation.The eluting gas that is fluidized-bed reactor is removed unreacted ammonia through neutralizing tower, with water at low temperature whole organic products is absorbed again.Absorption liquid is through extractive distillation, dehydrogenation cyanic acid and dewater high-purity propylene nitrile product.
Because the tungsten among the component Y is favourable to improving load, antimony and strontium can improve the performance of catalyst at high-response pressure, therefore remove some have negative effect to high pressure, high load capacity reactivity worth component, pay attention to the collocation of each catalyst component, catalyst has been had in that (WWH is 0.090 hour than high-response pressure (0.14MPa), higher load
-1) operational capacity under the condition, and the acrylonitrile once through yield has been up to 81.3% level, obtained effect preferably.
Activity of such catalysts of the present invention examination is to carry out in internal diameter is 38 millimeters fluidized-bed reactor.Loaded catalyst 550g, 440 ℃ of reaction temperatures, reaction pressure 0.14MPa, raw material proportioning (mole) is a propylene: ammonia: air=1: 1.2: 9.8, the propylene load (WWH) of catalyst is 0.090 hour
-1
Propylene conversion, acrylonitrile selectivity and once through yield are defined as follows in the present invention:
The invention will be further elaborated below by embodiment.[embodiment 1]
With 1.8 gram cesium nitrates, 1.49 gram potassium nitrate and 7.9 gram strontium nitrates mixing, add water 30 grams, the dissolving of heating back gets material (A); 18.7 gram chromium trioxides are dissolved in the 8.4 gram water, get material (B); 395.2 gram ammonium molybdates are dissolved in 50～90 ℃ of hot water of 325 grams, get material (C); 45.2 gram bismuth nitrates, 40.6 gram cerous nitrates, 119.6 are restrained magnesium nitrates, 314.7 gram nickel nitrates, 150.8 gram ferric nitrates, 8.96 gram antimony pentoxides and 0.97 gram germanium oxide mixing, add water 70 grams, the dissolving of heating back gets material (D).
With material (A) and 1250 gram weight concentration is that 40% Ludox mixes, under agitation add material (B) and (C) and (D), fully stir slurry, by well-established law the slurry of making is shaped to framboid in spray dryer, it is 89 millimeters at internal diameter at last, length be in the rotary roasting furnace of 1700 millimeters (89 * 1700 millimeters of φ) in 650 ℃ of roastings 1 hour, the catalyst of making consists of: 50%Mo
12Bi
0.5Fe
2.0Sb
0.3Sr
0.2Ni
5.8Mg
2.5Ce
0.5Cr
1.0Ge
0.05K
0.08Cs
0.05O
h[embodiment 2～9 and comparative example 1～3]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyst of forming in the following table, and, the results are shown in Table 1 with carrying out the reaction that ammoxidation of propylene generates acrylonitrile under the prepared catalyst reaction condition below.
The reaction condition of the foregoing description and comparative example is:
38 millimeters fluidized-bed reactors of φ
440 ℃ of reaction temperatures
Reaction pressure 0.14MPa
Loaded catalyst 550g
Catalyst propylene load (WWH) 0.090 hour
-1
Raw material proportioning (mole) C
3 =/ NH
3/ air=1/1.2/9.8
Table 1
| Embodiment | Catalyst is formed | Acrylonitrile yield % |
| Embodiment 1 | Mo 12Bi 0.5Fe 2.0Sb 0.3Sr 0.2Ni 5.8Mg 2.5Ce 0.5Cr 1.0Ge 0.05K 0.08Cs 0.05O h | 80.6 |
| Embodiment 2 | Mo 12Bi 0.5Fe 2.0Sb 0.3Sr 0.1Ni 5.8Mg 2.5Ce 0.5Cr 0.8W 0.5K 0.08Cs 0.05O h | 80.2 |
| Embodiment 3 | Mo 12Bi 0.5Fe 2.0Sb 0.3Sr 0.1Ni 5.8Mg 2.5Ce 0.5W 0.5Ge 0.1K 0.12Cs 0.05O h | 79.8 |
| Embodiment 4 | Mo 12Bi 0.5Fe 2.0Sb 0.1Sr 0.05Ni 6.0Mg 2.5Ce 0.5Cr 0.5W 0.35K 0.1Cs 0.15O h | 79.4 |
| Embodiment 5 | Mo 12Bi 0.8Fe 2.0Sb 0.1Sr 0.05Ni 6.0Mn 1.0Cr 0.5W 0.35Rb 0.05Cs 0.15O h | 81.3 |
| Embodiment 6 | Mo 12Bi 1.0Fe 2.0Sb 0.1Sr 0.05Ni 7.8Ce 0.5W 0.5Ge 0.25K 0.1Cs 0.2O h | 79.0 |
| Embodiment 7 | Mo 12Bi 0.5Fe 2.0Sb 0.3Sr 0.1Ni 7.8Ce 0.5Cr 0.8Ge 0.1W 0.35K 0.05Cs 0.1Tl 0.05O h | 80.5 |
| Embodiment 8 | Mo 12Bi 0.5Fe 2.0Sb 0.3Sr 0.1Ni 5.8Mg 2.5Ce 0.5Ge 0.1K 0.1Cs 0.05Tl 0.15O h | 81.0 |
| Embodiment 9 | Mo 12Bi 1.0Fe 2.0Sb 0.1Sr 0.5Ni 5.8Mg 2.5Cr 1.0Ge 0.05K 0.15Cs 0.05Tl 0.1O h | 80.8 |
| Comparative example 1 | Mo 12Bi 0.45Fe 1.8Ni 5.2Ce 0.45Na 0.15W 0.45Cr 0.45Mg 1.9K 0.15Cs 0.05O h | 77.2 |
| Comparative example 2 | Mo 12Bi 0.9Fe 1.8Ni 5.2Sr 0.15Na 0.15W 0.45Cr 0.45Mg 1.9K 0.05Cs 0.05O h | 76.9 |
| Comparative example 3 | Mo 12Bi 0.45Fe 1.8Ni 5.2Ce 0.45Na 0.15W 0.45Cr 0.45Mg 1.9K 0.20O h | 76.4 |
Claims (7)
1, a kind of fluidized bed catalyst for ammoxidation of propylene, form by silica supports with the following composition of atomic ratio measuring chemical formula:
Mo
12Bi
aFe
bSb
cSr
dX
eY
fZ
gO
h
X is selected among Co, Ni, Mn, Mg, Ca, Zn or the Cd at least a in the formula;
Y is selected among P, W, Ge, V, Cr, Ce, Pr, Nb or the Tb at least a;
Z is selected among alkali metal, In, Tl, Sm or the Te at least a;
The span of a is 0.01～3.0;
The span of b is 0.1～5.0;
The span of c is 0.01～2.0;
The span of d is 0.01～2.0;
The span of e is 0.1～12;
The span of f is 0.01～3.0;
The span of g is 0.01～1.5;
H satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein the amount of carrier silica is 30～70% by weight percentage in the catalyst.
2, according to the described fluidized bed catalyst for ammoxidation of propylene of claim 1, the span that it is characterized in that c is 0.05～1.0.
3, according to the described fluidized bed catalyst for ammoxidation of propylene of claim 1, the span that it is characterized in that d is 0.05～0.1.
4, according to the described fluidized bed catalyst for ammoxidation of propylene of claim 1, the span that it is characterized in that e is 0.1～10.0.
5, according to the described fluidized bed catalyst for ammoxidation of propylene of claim 1, the span that it is characterized in that f is 0.1～2.0.
6, according to the described fluidized bed catalyst for ammoxidation of propylene of claim 1, the span that it is characterized in that g is 0.05～1.0.
7, according to the described fluidized bed catalyst for ammoxidation of propylene of claim 1, the amount that it is characterized in that carrier silica in the catalyst is 40～60% by weight percentage.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113987A CN1100612C (en) | 1999-08-19 | 1999-08-19 | Fluidized bed catalyst for oxidation of propene ammonia |
| AU53871/00A AU5387100A (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for ammoxidation of propylene to acrylonitrile |
| PCT/CN2000/000167 WO2001014057A1 (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for ammoxidation of propylene to acrylonitrile |
| MXPA02001574A MXPA02001574A (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for ammoxidation of propylene to acrylonitrile. |
| BRPI0013338-8A BR0013338B1 (en) | 1999-08-19 | 2000-06-21 | fluidized bed catalyst for propylene amoxidation to acrylonitrile. |
| ROA200200166A RO120244B1 (en) | 1999-08-19 | 2000-06-21 | Fluidized bed catalyst for ammoxidation of propylene into acrylonitrile |
| JP2001518186A JP4095302B2 (en) | 1999-08-19 | 2000-06-21 | Fluidized bed catalyst for the ammoxidation of propylene to acrylonitrile. |
| DE10084931.8T DE10084931B3 (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for the ammoxidation of propylene to acrylonitrile |
| US09/642,289 US6420307B1 (en) | 1999-08-19 | 2000-08-18 | Fluidized-bed catalyst for propylene ammoxidation to acrylonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113987A CN1100612C (en) | 1999-08-19 | 1999-08-19 | Fluidized bed catalyst for oxidation of propene ammonia |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1285239A CN1285239A (en) | 2001-02-28 |
| CN1100612C true CN1100612C (en) | 2003-02-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113987A Expired - Lifetime CN1100612C (en) | 1999-08-19 | 1999-08-19 | Fluidized bed catalyst for oxidation of propene ammonia |
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| CN (1) | CN1100612C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408173C (en) * | 2005-08-15 | 2008-08-06 | 中国石油化工股份有限公司 | Acrylonitrile catalyst of containing calcium |
| CN100398204C (en) * | 2005-08-15 | 2008-07-02 | 中国石油化工股份有限公司 | Catalyst for producing acrylonitrile from ammoxidation of propylene |
| CN101279264B (en) * | 2007-04-04 | 2010-12-22 | 中国石油化工股份有限公司 | High load fluidized bed catalyst for preparing acrylonitrile |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0077675A1 (en) * | 1981-10-20 | 1983-04-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for the oxidation or ammoxidation of propylene, isobutylene, tert-butanol or 1-butene |
| CN1053197A (en) * | 1990-01-09 | 1991-07-24 | 标准石油公司 | The production method of acrylonitrile and methacrylonitrile |
| CN1172690A (en) * | 1996-08-06 | 1998-02-11 | 中国石油化工总公司 | Acrylonitrile fluidized bed catalyst prepared by propene ammonia oxidation |
| JPH10156185A (en) * | 1996-08-06 | 1998-06-16 | China Petro Chem Corp | Catalyst for ammoxidation of propylene to acrylonitrile |
| JP3058962B2 (en) * | 1991-11-28 | 2000-07-04 | サンデン株式会社 | Compressor |
-
1999
- 1999-08-19 CN CN99113987A patent/CN1100612C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0077675A1 (en) * | 1981-10-20 | 1983-04-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for the oxidation or ammoxidation of propylene, isobutylene, tert-butanol or 1-butene |
| CN1053197A (en) * | 1990-01-09 | 1991-07-24 | 标准石油公司 | The production method of acrylonitrile and methacrylonitrile |
| JP3058962B2 (en) * | 1991-11-28 | 2000-07-04 | サンデン株式会社 | Compressor |
| CN1172690A (en) * | 1996-08-06 | 1998-02-11 | 中国石油化工总公司 | Acrylonitrile fluidized bed catalyst prepared by propene ammonia oxidation |
| JPH10156185A (en) * | 1996-08-06 | 1998-06-16 | China Petro Chem Corp | Catalyst for ammoxidation of propylene to acrylonitrile |
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|---|---|
| CN1285239A (en) | 2001-02-28 |
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